Process for dyeing or printing textile fibre materials with gloss pigments

ABSTRACT

The present invention relates to a process for dyeing or printing textile fibre materials, wherein a gloss pigment A or B is used comprising A(a) a core consisting of a substantially transparent or metallically reflecting material and A(b) at least one coating substantially consisting of one or more silicon oxides wherein the molar ratio of oxygen to silicon is on average from 0.03 to 0.95, or B(a) a core substantially consisting of one or more silicon oxides wherein the molar ratio of oxygen to silicon is on average from 0.03 to 0.95.

The present invention relates to a process for dyeing or printing fibrematerial with coloured gloss pigments by the pigment dyeing or pigmentprinting process.

Gloss pigments are effect pigments, that is to say reflecting flatparticles whose radiation reflection is of different brightness and/orhas a different reflection spectrum depending on the angle to the flatsurface. In a surface coated using effect pigments, for example, theeffect pigment particles tend to be oriented, within the surfacecoating, substantially parallel to the surface with the result that thecoloured surface of the coating, when illuminated from a fixed whitelight source, is capable of exhibiting different colours depending onthe viewing angle and the nature of the effect pigment.

A very large proportion of the light incident on an effect pigment isreflected but a relatively small portion thereof is absorbed. Applyingthin layers to the flat pigment core gives rise to interferencephenomena, the intensity and spectrum of the reflected ray varyingaccording to the angle of incidence and the viewing angle.

The present invention relates to a process for dyeing or printingtextile fibre materials, wherein a gloss pigment A or B is usedcomprising

-   -   A(a) a core consisting of a substantially transparent or        metallically reflecting material and    -   A(b) at least one coating substantially consisting of one or        more silicon oxides wherein the molar ratio of oxygen to silicon        is on average from 0.03 to 0.95, or    -   B(a) a core substantially consisting of one or more silicon        oxides wherein the molar ratio of oxygen to silicon is on        average from 0.03 to 0.95.

The gloss pigments A or B used according to the invention are in generalparticles having a length of from 2 μm to 5 mm, a width of from 2 μm to2 mm and a thickness of from 20 nm to 1.5 μm, and a length to thicknessratio of at least 2:1, the particles having a core with twosubstantially parallel faces, the distance between which faces is theshortest axis of the core.

In the case of the gloss pigments A, the core consists of asubstantially transparent or metallically reflecting material having,applied to the parallel faces thereof, an SiO_(x) layer wherein0.03≦x≦0.95 and optionally further layers.

In the case of the gloss pigments B, the core is composed of SiO_(x)wherein 0.03≦x≦0.95, optionally having one or more further layersapplied to the parallel faces thereof.

The further layers may cover the parallel faces or the entire surface.

The gloss pigment A used according to the invention preferably has thefollowing layer structure:

When the core A(a) consists of a metallically reflecting material, thatmaterial is preferably selected from Ag, Al, Au, Cu, Cr, Ge, Mo, Ni, Si,Ti, Zn, alloys thereof, graphite, Fe₂O₃ and MoS₂. Special preference isgiven to Al.

When the core A(a) consists of a transparent material, the material ispreferably selected from mica, SiO_(y) wherein y is from 0.95 to 1.8,SiO₂ or SiO₂/TiO₂ mixtures. Special preference is given to SiO_(y) orsilicon dioxide.

The material of the coating A(d) is advantageously a metal oxide, suchas, for example, TiO₂, ZrO₂, SiO, SiO₂, SnO₂, GeO₂, ZnO, Al₂O₃, V₂O₅,Fe₂O₃, Cr₂O₃, PbTiO₃ or CuO, or a mixture thereof.

In a preferred embodiment, the gloss pigment A used according to theinvention has the following layer structure:SiO₂/SiO_(x)/SiO_(y)/SiO_(x)/SiO₂, SiO₂/SiO_(x)/SiO₂/SiO_(x)/SiO₂,SiO₂/SiO_(x)/Al/SiO_(x)/SiO₂, TiO₂/SiO₂/SiO_(x)/SiO₂/SiO_(x)/SiO₂/TiO₂or TiO₂/SiO₂/SiO_(x)/Al/SiO_(x)/SiO₂/TiO₂, wherein x is from 0.03 to0.95 and y is from 0.95 to 1.8.

The core A(a) is a platelet having an average diameter of from 1 to 50μm and a thickness of from 20 to 500 nm.

The thickness of the SiO_(x) layer A(b) is generally from 5 to 200 nm,preferably from 5 to 100 nm.

The thickness of the SiO₂ layer A(c) is generally from 1 to 200 nm,preferably from 2 to 100 nm.

The thickness of the TiO₂ layer A(d) is generally from 1 to 200 nm,preferably from 10 to 150 nm.

Preferably, the SiO_(x), SiO₂ and TiO₂ layers arrangedmirror-symmetrically with respect to the core of Al, SiO_(y) or SiO₂each have the same layer thickness. In a further embodiment, the supportlayer may be surrounded on both sides by metal oxides having differentlayer thicknesses.

Especially preferably, the gloss pigment A used according to theinvention has the following layer structure:SiO₂/SiO_(x)/SiO_(y)/SiO_(x)/SiO₂, SiO₂/SiO_(x)/SiO₂/SiO_(x)/SiO₂ orTiO₂/SiO₂/SiO_(x)/SiO₂/SiO_(x)/SiO₂/TiO₂, wherein x is from 0.03 to0.95, preferably from 0.05 to 0.5, and y is from 0.95 to 1.8, preferablyfrom 1.1 to 1.5, the core is a platelet having an average diameter offrom 1 to 50 μm and a thickness of from 20 to 500 nm, the thickness ofthe SiO_(x) layer is from 5 to 200 nm, preferably from 5 to 100 nm, thethickness of the SiO_(y) or SiO₂ layer is from 1 to 200 nm, preferablyfrom 2 to 100 nm, and the thickness of the TiO₂ layer is from 1 to 180nm, preferably from 50 to 160 nm.

The platelet-shaped or plane-parallel gloss pigments A having a coreA(a) of SiO_(y) wherein 0.95≦y≦1.8, preferably wherein 1.1≦y≦1.5, areobtained by means of a process comprising the following steps:

-   -   i) vapour-deposition of a separating agent onto a (movable)        carrier to produce a separating agent layer,    -   ii) vapour-deposition of an SiO_(x) layer (0.03≦x≦0.95) onto the        separating agent layer,    -   iii) vapour-deposition of an SiO_(y) layer (0.95≦y≦1.8) onto the        SiO_(x) layer obtained in step ii),    -   iv) vapour-deposition of an SiO_(x) layer (0.03≦x≦0.95) onto the        SiO_(y) layer obtained in step iii),    -   v) dissolution of the separating agent layer in a solvent,    -   vi) separation of the gloss pigment from the solvent,        the SiO_(y) layer in step iii) being vapour-deposited from a        vaporiser containing a charge comprising a mixture of Si and        SiO₂, SiO_(y) or a mixture thereof, and the SiO_(x) layer being        vapour-deposited from a vaporiser charged with silicon.

The process mentioned above makes available gloss pigments A which,compared with natural mica effect pigments and with effect pigmentsproduced in wet procedures, have a high degree of plane parallelism anda defined thickness in the range of ±10%, preferably ±5%, of the averagethickness.

The separating agent condensed onto the carrier may be a surfacecoating, an organic substance soluble in organic solvents or water andvaporisable in vacuo, such as anthracene, anthraquinone,acetamidophenol, acetylsalicylic acid, camphoric anhydride,benzimidazole, benzene-1,2,4-tricarboxylic acid,biphenyl-2,2-dicarboxylic acid, bis(4-hydroxyphenyl)sulfone,dihydroxyanthraquinone, hydantoin, 3-hydroxybenzoic acid,8-hydroxyquinoline-5-sulfonic acid monohydrate, 4-hydroxycoumarin,7-hydroxycoumarin, 3-hydroxynaphthalene-2-carboxylic acid, isophthalicacid, 4,4-methylene-bis-3-hydroxynaphthalene-2-carboxylic acid,naphthalene-1,8-dicarboxylic anhydride, phthalimide and its potassiumsalt, phenolphthalein, phenothiazine, saccharin and its salts,tetraphenylmethane, triphenylene, triphenylmethanol or a mixture of atleast two of those substances. The separating agent is preferably aninorganic salt soluble in water and vaporisable in vacuo (see, forexample, DE 198 44 357), such as sodium chloride, potassium chloride,lithium chloride, sodium fluoride, potassium fluoride, lithium fluoride,calcium fluoride, sodium aluminium fluoride and disodium tetraborate.

The SiO_(y) layer is obtained by heating a preferably stoichiometricmixture of fine silicon and quartz (SiO₂) powder in a vaporiserdescribed, for example, in DE 43 42 574 C1 and in U.S. Pat. No.6,202,591 to more than 1300° C. under a high vacuum. The reactionproduct is silicon monoxide gas, which under vacuum is directed directlyonto the passing carrier, where it condenses as SiO. Non-stoichiometricmixtures may also be used. The vaporiser contains a charge comprising amixture of Si and SiO₂, SiO_(y), or a mixture thereof, the particle sizeof the substances that react with one another (Si and SiO₂) beingadvantageously less than 0.3 mm. The weight ratio of Si to SiO₂ isadvantageously in the range from 0.15:1 to 0.75:1 (parts by weight);preferably, a stoichiometric mixture is present. SiO_(x) present in thevaporiser vaporises directly. Si and SiO₂ react at a temperature of morethan 1300° C. to form silicon monoxide vapour.

According to the invention, step v) is carried out at a pressure that ishigher than the pressure in steps i) to iv) and lower than atmosphericpressure.

The (movable) carrier preferably comprises one or more continuous metalbelts, with or without a polymer coating, or one or more polyimide orpolyethylene terephthalate belts. The (movable) carrier may furthermorecomprise one or more discs, cylinders or other rotationally symmetricalbodies, which rotate about an axis.

The gloss pigments are separated from the solvent of the separatingagent preferably by washing-out and subsequent filtration,sedimentation, centrifugation, decanting or evaporation. Furthermore,the gloss pigments may, after washing-out of the dissolved separatingagent contained in the solvent, be frozen together with the solvent andsubsequently subjected to a process of freeze-drying, whereupon thesolvent is separated off as a result of sublimation below the triplepoint and the dry product remains behind in the form of individualplane-parallel structures.

The silicon suboxide condensed on the movable carrier starting fromvaporised SiO corresponds to the formula SiO_(y) wherein 0.95≦y≦1.8,preferably wherein 1.1≦y≦1.5, y values of less than 1 being obtained bymeans of an excess of silicon in the vaporiser material. Except under anultra-high vacuum, in industrial vacuums of a few 10⁻² Pa vaporised SiOalways condenses as SiO_(y) wherein 1≦y≦1.8, especially wherein1.1≦y≦1.5, because high-vacuum apparatuses always contain, as a resultof gas emission from surfaces, traces of water vapour which react withthe readily reactive SiO at vaporisation temperature. The SiO_(y) layerscan be converted into SiO₂ layers by means of oxidative heat treatment.

If, under industrial vacuums of a few 10⁻² Pa, Si is vaporised insteadof SiO, silicon oxides that have a less-than-equimolar oxygen contentare obtained, that is to say SiO_(x) wherein 0.03≦x≦0.95, especially0.05≦x≦0.5, most especially 0.1≦x≦0.3, which have astonishingly highstability to oxidation along with a high refractive index, even in thinlayers. Heating in the presence of oxygen at from 150 to 500° C.,preferably from 175 to 300° C., unexpectedly results in a very thin, forexample approximately 20 nm thick, superficial silicon dioxide layer,which is a very convenient method of producing structures having thelayer sequence SiO₂/SiO_(x)/SiO₂/SiO_(x)/SiO₂. If thicker silicondioxide layers are desired, they may conveniently be produced, asdescribed above, by means of vapour-deposition of SiO_(y) and oxidativeheat treatment thereof.

In detail, a salt, for example NaCl, followed by the layers of SiO_(x)and SiO_(y) are successively vapour-deposited onto a carrier, which maybe a continuous metal belt, passing by way of the vaporisers under avacuum of <0.5 Pa, the vapour-deposited thicknesses of salt beingapproximately from 20 to 100 nm, preferably from 30 to 60 nm. On itsfurther course, the belt-form carrier, which is closed to form a loop,runs through dynamic vacuum lock chambers of known construction (cf.U.S. Pat. No. 6,270,840) into a region of from 1 to 5×10⁴ Pa pressure,preferably from 600 to 10⁹ Pa pressure, and especially from 10³ to 5×10³Pa pressure, where it is immersed in a separating bath. The temperatureof the solvent should be so selected that its vapour pressure is in theindicated pressure range. With mechanical assistance, the separatingagent layer rapidly dissolves and the product layer breaks up intoflakes, which are then in the form of a suspension in the solvent. Onits further course, the belt is dried and freed from any contaminantsstill adhering to it. It runs through a second group of dynamic vacuumlock chambers back into the vaporisation chamber, where the process ofcoating with separating agent and product layer is repeated.

The suspension then obtained in both cases, comprising productstructures and solvent with separating agent dissolved therein, is thenseparated in a further operation in accordance with a known technique.For that purpose, the product structures are first concentrated in theliquid and rinsed several times with fresh solvent in order to wash outthe dissolved separating agent. The product, in the form of a solid thatis still wet, is then separated off by means of filtration,sedimentation, centrifugation, decanting or evaporation.

After drying, the product can be subjected to oxidative heat treatment,in which SiO_(y) is converted to SiO₂. Known methods are available forthat purpose. Air or some other oxygen-containing gas is passed throughthe plane-parallel structures, which are in the form of loose materialor in a fluidised bed, for several hours at a temperature of more than200° C., preferably more than 400° C. and especially from 500 to 1000°C. The product can then be brought to the desired particle size by meansof grinding or air-sieving and delivered for further use.

It is possible to arrange a plurality of separating agent and productvaporisers one after another in the running direction of the belt in thevaporisation zone. By that means there is obtained, with littleadditional outlay in terms of apparatus, a layer sequence of S+P+S+P,wherein S is the separating agent layer and P is the product layer. Ifthe number of vaporisers is doubled and the belt speed is the same,twice the amount of product will obtained.

Separating off the plane-parallel structures after washing-out atatmospheric pressure can be carried out under gentle conditions byfreezing the suspension, which has been concentrated to a solids contentof approximately 50%, and subjecting it in known manner to freeze-dryingat approximately −10° C. and 50 Pa pressure. The dry substance remainsbehind as product, which can be subjected to the steps of furtherprocessing by means of coating or chemical conversion.

Instead of using a continuous belt, it is possible to produce theproduct by carrying out the steps of vapour-deposition of separatingagent and SiO, of separation, and of drying the carrier, in an apparatushaving a rotary body, in accordance with DE 199 52 032. The rotary bodymay be one or more discs, a cylinder or any other rotationallysymmetrical body.

The process described hereinbefore makes it possible to produce glosspigments with a high production rate, having very good stabilityproperties and being distinguished by a wide range of possible hues withhigh colour saturation and covering power.

The gloss pigments produced in accordance with the process describedabove have, especially, a high degree of colour purity and gloss and arehighly shear-stable. The pigment platelets separated from the carrierhave, with respect to one another, substantially identical andreproducible optical properties, such as, for example, the same hue whenviewed from a particular angle, because the thickness of the colours canbe readily controlled.

The optional coating with TiO₂ can result in more intense colours and ispreferably applied by precipitation by wet chemical means.

The titanium oxide layers are obtainable, for example, analogously to amethod described in DE 195 01 307, by producing the titanium oxide layerby controlled hydrolysis of one or more titanic acid esters, whereappropriate in the presence of an organic solvent and a basic catalyst,by means of a sol-gel process. Suitable basic catalysts are, forexample, amines, such as triethylamine, ethylenediamine, tributylamine,dimethylethanolamine and methoxy-propylamine. The organic solvent is awater-miscible organic solvent, such as a C₁₋₄alcohol, especiallyisopropanol.

Suitable titanic acid esters are selected from the group comprisingalkyl and aryl alcoholates, carboxylates, and carboxyl-radical- oralkyl-radical- or aryl-radical-substituted alkyl alcoholates orcarboxylates of titanium. The use of tetraisopropyl titanate ispreferred. In addition, acetylacetonates and acetoacetylacetonates oftitanium, such as titanium acetylacetonate, may be used. According to anembodiment of the present invention, the process described in U.S. Pat.No. 3,553,001 is used for application of the titanium dioxide layers.

An aqueous titanium salt solution is slowly added to a suspension of thematerial being coated, which suspension has been heated to approximately50-100° C., especially 70-80° C., and a substantially constant pH valueof approximately from 0.5 to 5, especially approximately from 1.2 to2.5, is maintained by simultaneously metering in a base, such as, forexample, aqueous ammonia solution or aqueous alkali metal hydroxidesolution. As soon as the desired layer thickness of precipitated TiO₂has been achieved, the addition of titanium salt solution and base isstopped.

That process, also referred to as a titration process, is distinguishedby the fact that an excess of titanium salt is avoided. That is achievedby feeding in for hydrolysis, per unit of time, only that amount whichis necessary for even coating with the hydrated TiO₂ and which can betaken up per unit of time by the available surface of the particlesbeing coated. In principle, the anatase form of TiO₂ forms on thesurface of the starting pigment. By adding small amounts of SnO₂,however, it is possible to force the rutile structure to be formed. Forexample, as described in WO 93/08237, tin dioxide can be depositedbefore titanium dioxide precipitation.

Where appropriate, an SiO₂ protective layer can be applied on top of thetitanium dioxide layer, for which the following method may be used: Asoda waterglass solution is metered in to a suspension of the materialbeing coated, which suspension has been heated to approximately 50-100°C., especially 70-80° C. The pH is maintained at from 4 to 10,preferably from 6.5 to 8.5, by simultaneously adding 10% hydrochloricacid. After addition of the waterglass solution, stirring is carried outfor a further 30 minutes.

It is possible to obtain pigments that are more intense in colour andmore transparent by applying, on top of the TiO₂ layer, a metal oxide oflow refractive index, such as SiO₂, Al₂O₃, AlOOH, B₂O₃ or a mixturethereof, preferably SiO₂, and applying a further TiO₂ layer on top ofthe latter layer.

It is furthermore possible to subject the finished pigment to subsequentcoating or subsequent treatment, which further increases the light,weather and chemical stability or which facilitates handling of thepigment, especially its incorporation into various media. For example,the procedures described in DE 22 15 191, DE 31 51 354, DE 32 35 017 orDE 33 34 598 are suitable as subsequent treatment or subsequent coating.

The core B(a) of gloss pigment B preferably has a thickness of from 20to 350 nm.

One or more further layers are optionally applied to the parallel facesof the core B(a) of gloss pigment B of SiO_(x).

In one embodiment of the gloss pigment B used according to theinvention, there is applied to the core B(a) a layer B(b) having athickness of from 0 to 500 nm, comprising from 17 to 51 atom % siliconbonded to more than 95 atom % oxygen, based on 100 atom % silicon.

In further embodiments of the gloss pigment B used according to theinvention there is applied either directly to the core B(a) or to thelayer B(b) of the above-mentioned embodiment a layer B(c) having athickness of from 0 to 300 nm, that has a transparency of from 50 to100% and a complex refractive index n+ik satisfying the condition√{square root over (n²+k²)}≧1.5 at the wavelength of maximum visiblereflection of the particles, and that substantially consists of carbon,an organic compound, a metal, a dielectric or a mixture thereof.

The layers B(b) and/or B(c) are preferably arranged symmetrically aboutthe core B(a), both as regards composition and as regards layerthickness.

In addition to the optionally present layers B(b) and/or B(c), furtherlayers may also be present.

The gloss pigments B used according to the invention preferably compriseparticles having at least one layer B(b) and B(c), preferably particleshaving at least one layer B(b) and especially also those having both alayer B(c) and a layer B(b). Special preference is given, therefore, toparticles having the layer sequences B(b)-B(a)-B(b) andB(c)-B(b)-B(a)-B(b)-B(c).

The gloss pigment particles B preferably have lengths and widths of from5 to 20 μm and thicknesses of from 60 nm to 1.0 μm.

The core B(a) preferably comprises from 60 to 93 atom %, and especiallyfrom 65 to 91 atom %, silicon. The silicon in the core B(a) ispreferably bonded to from 5 to 50 atom % oxygen and especially to from10 to 30 atom % oxygen, based on 100 atom % silicon.

The core B(b) preferably has a thickness of from 20 to 250 nm andpreferably comprises from 20 to 40 atom % silicon bonded to more than150 atom % oxygen per 100 atom % silicon, especially from 30 to 36 atom% silicon bonded to more than 178 atom % oxygen per 100 atom % silicon.Most preferably, at least 90 atom % of the layer B(b) consists of SiO₂.

The layer B(c) preferably has a thickness of from 20 to 250 nm andespecially from 30 to 100 nm.

The layers B(b) and B(c) need not be present but offer advantages, bothon an individual basis and in combination, with regard to colourcharacteristics and stability. Further layers may optionally be appliedto the said layers. The layer B(c) offers useful practical advantagesespecially when it is applied as the final layer in thevapour-deposition process or is formed immediately aftervapour-deposition. Further layers may then be applied using simpler, forexample chemical, methods.

It is also possible to produce particles, for example, having the layersequence B(c)-B(a)-B(c). Useful materials for the layer B(c) are, forexample, metals such as Ag, Al, Au, Cu, Co, Cr, Fe, Ge, Mo, Nb, Ni, Si,Ti, V, alloys thereof, inorganic or organic pigments or colorants,graphite and compounds similar to graphite as disclosed in EP 0 982 376,metal oxides such as MoS₂, TiO₂, ZrO₂, SiO, SiO₂, SnO₂, GeO₂, ZnO,Al₂O₃, V₂O₅, Fe₂O₃, Cr₂O₃, PbTiO₃ or CuO, and mixtures thereof. Thelayer B(c) may, however, also consist of, for example, any one of themany dielectric materials whose resistivity according to theconventional definition is at least 10¹⁰ Ω·cm, which are likewise verywell known to the person skilled in the art.

The transparency of the layer B(c) is advantageously at least 50%,corresponding to a reflectivity of at most 50%. With a metal, theskilled person will know how to achieve this by means of appropriatelythin layers, for example using up to approximately 3 nm of Al or Au orup to approximately 10 nm of Co or Cu. In the case of colourless orcoloured dielectrics greater thicknesses are possible.

Silicon oxides having a less-than-equimolar oxygen content (SiO_(x)wherein 0.03≦x≦0.95, especially 0.05≦x≦0.5, more especially 0.1≦x≦0.3)have astonishingly high stability to oxidation along with a highrefractive index, even in thin layers. Hydrolysis or heating in thepresence of oxygen at from 150 to 500° C., preferably from 200 to 300°C., unexpectedly results in a very thin, for example approximately 20 nmthick, superficial silicon dioxide layer, which is a very convenientmethod of producing structures having the layer sequence B(b)-B(a)-B(b).If thicker silicon dioxide layers are desired, they can be convenientlyproduced analogously to the method of the second implementation exampleof WO 00/43565 by means of vapour-deposition of silicon monoxide andsubsequent heat-treatment. It is advantageous therein that the layer ofsilicon oxide lying underneath the silicon monoxide and having aless-than-equimolar oxygen content remains unchanged.

Further layers may subsequently be applied to structures having thelayer sequence B(b)-B(a)-B(b), for example in order to obtainB(c)-B(b)-B(a)-B(b)-B(c), which may be produced especially convenientlyby wet-chemical application of a layer B(c) onto structures having thelayer sequence B(b)-B(a)-B(b).

The core B(a) is produced, for example, by vapour-deposition onto amedium that can be readily dissolved away subsequently, as disclosed,for example, in DE 19 844 357, EP 0 990 715, U.S. Pat. No. 5,135,812,U.S. Pat. No. 6,270,840, WO 93/08237, WO 00/18978, WO 01/57287 or any ofthe references cited therein. For vapour-depositing the core B(a) thereis advantageously used metallic silicon, which need not be of highpurity. It is preferable to use silicon having a content of less than99.999% by weight Si, for example from 50 to 99.9% by weight Si,especially from 55 to 99% by weight Si, more especially from 60 to 98%by weight Si, very especially from 65 to 90% by weight Si. Impuritiesmay be present, for example elements of the main groups 13, 14 and 15and/or transition elements, such as Fe, Al, Ge, Sn and/or Sb.

The layers B(b) or B(c) may also be produced, for example, byvapour-deposition, commencing in this case—for symmetricalstructures—with vapour-deposition of the layer B(b) or B(c), onto whichthe core and then a further layer B(b) or B(c) are vapour-deposited.

The vapour-deposition and isolation of the vapour-deposited layers areadvantageously carried out in accordance with the process describedabove for gloss pigments A.

Gloss pigments A and B are described in U.S. Pat. No. 5,766,335, SwissPatent Application No. 1334/02 and European Patent Applications No. EP02 405 749.9 and No. EP 03 405 024.5. Gloss pigments A and B can be usedin the process according to the invention on their own or in admixture.It is also possible to use mixtures of gloss pigments A and/or B withother effect pigments.

The gloss pigments used according to the invention are goniochromaticand result in brilliant, highly saturated (lustrous) colours. They aretherefore very especially suitable for combination with conventional,transparent pigments, for example organic pigments, such as, forexample, diketopyrrolopyrroles, quinacridones, dioxazines, perylenes,isoindolinones etc. The transparent pigment may have a similar colour tothe effect pigment. Especially interesting combination effects areobtained, however, analogously to EP 0 388 932 or EP 0 402 943 forexample, when the colour of the transparent pigment and that of theeffect pigment are complementary.

The process according to the invention is carried out in accordance withknown textile dyeing and printing processes using conventional pigmentsas described, for example, in Textile Chemist and Colorist 25 (1993)31-37.

The gloss pigments and the conventional pigments optionally combinedtherewith are advantageously used in the dyeing preparations, forexample dye baths or printing pastes, in dispersed form.

During dispersion of the effect pigments used according to the inventionand during processing thereof, conditions under which only relativelyweak shearing forces occur are preferably maintained so that the effectpigment will not be broken up into smaller fragments. The permissibleshear force approximately corresponds to that which is permissible forthe core, the gentle dispersion of which in a high-molecular-weightorganic material is generally well-known to the person skilled in theart.

The customary dispersants, preferably non-ionic dispersants, can be usedfor the preparation of the dispersions.

Suitable binders for the process according to the invention include thepigment dyestuff binders customarily employed in textile dyeing andtextile printing, for example acrylate-based, urethane-based orbutadiene-based binders. Such binders are known to the person skilled inthe art.

Suitable acrylate binders are, for example, acrylic polymers, such as,for example, poly(meth)acrylates, or mixed polymers of (meth)acrylateswith suitable comonomers, such as, for example, acrylic, methacrylic,maleic, fumaric, itaconic, mesaconic, citraconic, vinyl-acetic,vinyloxyacetic, vinylpropionic, crotonic, aconitic, allylacetic,allyloxyacetic, allyl-malonic, 2-acrylamido-2-methylpropanesufonic,glutaconic or allylsuccinic acid, or with esters of those acids,(meth)acrylamide, N-vinylpyrrolidone, N-vinylformamide,N-vinylacetamide, (meth)acrolein, N-vinyl-N-methylacetamide,vinylcaprolactam, styrene derivatives or vinyl-phosphonic acid;polyamide derivatives; synthetic resin dispersions; vinyl-based mixedpolymers; diamide/aldehyde precondensates; mixed polymers comprisingN-vinyllactam or butadiene-based polymers. Suitable acrylate binders aresoluble in aqueous medium or in aqueous medium containing water-miscibleorganic solvents, where applicable with the addition of bases. The saidacrylate binders are preferably used in the form of an aqueousformulation. Such acrylate binders are commercially available in acidicform or in partially or completely neutralised form, for example Primal®(Rohm & Haas), Neocryl® (NeoResins), Carbocet® (BF Goodrich), Joncryl®(Johnson Polymers) or ALCOPRINT® (Ciba Specialty Chemicals) binders.

According to an embodiment of the present invention, the dyeingpreparation, for example the printing paste or the dye bath, is preparedby using a concentrated formulation comprising the gloss pigment and thebinder. Such formulations will preferably be aqueous formulations. Theweight ratio between gloss pigment and binder is preferably from 1:1 to1:50, especially from 1:1 to 1:10. A weight ratio of from 1:1 to 1:5 isespecially preferred. The gloss pigment is present in the formulationpreferably in an amount of from 2 to 80 g/kg, especially in an amount offrom 5 to 50 g/kg. The binder is present in the formulation preferablyin an amount of from 20 to 200 g/kg, especially in an amount of from 30to 150 g/kg.

The dyeing preparations may additionally comprise further auxiliariescustomarily used, for example, in pigment printing, for examplecrosslinkers.

Suitable crosslinkers are, for example, water-soluble melamine,formaldehyde/melamine and formaldehyde/urea resins or precondensates,such as trimethylolmelamine, hexamethylol-melamine or dimethylol urea,or water-soluble formaldehyde (pre)condensation products with formamide,thiourea, guanidine, cyanamide, dicyandiamide and/or water-solubleorganic sulfonates, such as, for example, the sodium salt ofnaphthalenesulfonic acid, or glyoxalic urea derivatives, such as, forexample, the compound of formula

and especially N-methylol derivatives of nitrogen-containing compounds,such as, for example, non-etherified or etherified melamine/formaldehydecondensation products or N-methylol urea compounds.

Examples of non-etherified or etherified melamine/formaldehydecondensation products are the compounds of formulae

The non-etherified or etherified N-methylol urea compounds are, forexample, reaction products of formaldehyde with urea or ureaderivatives, which reaction products may have been subsequentlyetherified, suitable urea derivatives being, for example, cyclicethylene or propylene ureas that may also contain substituents such ashydroxyl groups in the alkylene group, urones or unsubstituted orsubstituted triazone resins.

Examples of corresponding N-methylol urea compounds are unmodified ormodified N-methylolhydroxyethylene urea products, for example thecompounds of formula

or methylolation products based on propylene urea or ethyleneurea/melamine.

Preferred crosslinkers are unmodified or modifiedN-methylolhydroxyethylene urea compounds, methylolation products basedon propylene urea or ethylene urea/melamine and, especially,non-etherified or etherified melamine/formaldehyde condensationproducts. It is also possible to use mixtures of two or more differentwater-soluble crosslinkers, for example a mixture consisting of anon-etherified and an only partially etherified melamine/formaldehydecondensation product.

Suitable crosslinkers are known commercially, for example under the nameALCOPRINT® (Ciba Specialty Chemicals).

If desired, crosslinking catalysts may additionally be used.

Suitable crosslinking catalysts for the process according to theinvention are, for example, any agents customarily used as catalysts fornon-crease and non-crumple finishes, as are known fromTextilhilfsmittelkatalog 1991, Konradin Verlag R. Kohlhammer,Leinfelden-Echterdingen 1991. Examples of suitable crosslinkingcatalysts are inorganic acids, for example phosphoric acid; Lewis acids,for example zinc chloride, zirconium oxychloride, NaBF₄, AlCl₃, MgCl₂;ammonium salts, for example ammonium sulfate, ammonium chloride; orhydrohalides, especially hydrochlorides of organic amines, for exampleCH₃—CH₂—CH₂—NH—CH₃. HCl. Preference is given to the use of ammoniumsalts or magnesium-containing Lewis acids and, especially, to the use ofammonium chloride or magnesium chloride.

To increase the softness of the dyed or printed fibre material and thusto obtain a particular handle, the dyeing preparations used according tothe invention may additionally comprise a fabric softener. Fabricsofteners are known in the textile industry. They are non-ionic,anionic-active, cationic or amphoteric softeners. Emulsions ofsilicones, mostly high-molecular-weight α,ω-dimethylpolysiloxane, occupya special position. Fabric softeners based on silicone emulsions arepreferred. Such fabric softeners are commercially available, for exampleunder the name AVIVAN® or ULTRATEX® (Ciba Specialty Chemicals).

If desired, the dyeing preparation may additionally comprise acid donorssuch as butyro-lactone or sodium hydrogen phosphate, preservatives,sequestering agents, emulsifiers, water-insoluble solvents, oxidisingagents or deaerating agents.

Suitable preservatives are especially formaldehyde-yielding agents, suchas, for example, paraformaldehyde and trioxane, especially aqueous,approximately from 30 to 40% by weight formaldehyde solutions; suitablesequestering agents are, for example, nitrolotriacetic acid sodium,ethylenediaminetraacetic acid sodium, especially sodiumpolymetaphosphate, more especially sodium hexametaphosphate; suitableemulsifiers are especially adducts of an alkylene oxide and a fattyalcohol, especially an adduct of oleyl alcohol and ethylene oxide;suitable water-insoluble solvents are high boiling, saturatedhydrocarbons, especially paraffins having a boiling range ofapproximately from 160 to 210° C. (so-called white spirit); a suitableoxidising agent is, for example, an aromatic nitro compound, especiallyan aromatic mono- or di-nitro-carboxylic or -sulfonic acid which may bein the form of an alkylene oxide adduct, especially anitrobenzenesulfonic acid; and suitable deaerating agents are, forexample, high boiling solvents, especially turpentine oils, higheralcohols, preferably C₈-C₁₀alcohols, terpene alcohols or deaeratingagents based on mineral oils and/or silicone oils, especially commercialformulations composed of approximately from 15 to 25% by weight of amineral oil and silicone oil mixture and approximately from 75 to 85% byweight of a C₈ alcohol, such as, for example, 2-ethyl-n-hexanol.

The dyeing preparations can be applied to the fibre materials by variousmethods, especially in the form of aqueous dye baths and printingpastes. They are especially suitable for dyeing by the pad dyeingprocess and for printing. Printing is preferred.

Other suitable processes are the foam dyeing process, the spray dyeingprocess and printing by the ink-jet printing process or by the chromojetprocess which is used, for example, in carpet printing.

The amounts in which the gloss pigments are used in the dyeing baths orprinting pastes may vary depending upon the desired depth of colour; ingeneral, amounts of from 0.01 to 15% by weight, especially from 0.1 to10% by weight, based on the weight of the material being dyed, and from0.05 to 200 g, especially from 1.0 to 100 g, of gloss pigments per kg ofprinting paste have proved advantageous.

According to a preferred embodiment of the present invention, the dyeingpreparation is made by first preparing a formulation comprising all thecomponents with the exception of the gloss pigment. The gloss pigment isthen incorporated into the formulation in the required quantity. Theratios by weight and the quantity information given above apply in thiscase.

Preferably, the dyeing preparations according to the invention are usedin the form of a printing paste.

The printing paste usually comprises from 1 to 400 g, especially from 20to 250 g, of binder per kg of printing paste.

In addition to comprising gloss pigment and binder, the printing pasteadvantageously comprises thickeners of synthetic origin, such as, forexample, those based on poly(meth)acrylic acids, poly(meth)acrylamides,and their copolymers and terpolymers.

Thickeners based on potassium or sodium salts of poly(meth)acrylic acidsare preferably used since the addition of ammonia or ammonium salts canadvantageously be partially or completely dispensed with when suchthickeners are used.

Examples of other thickeners are commercial alginate thickenings, starchethers, locust bean flour ethers and cellulose ethers. Suitablecellulose ethers are, for example, methyl-, ethyl-, carboxymethyl-,hydroxyethyl-, methylhydroxyethyl-, hydroxypropyl- andhydroxypropyl-methyl-cellulose. Suitable alginates are especially alkalimetal alginates and preferably sodium alginate.

In printing of the fibre material, the printing paste is applieddirectly to the fibre material over the entire surface or in places,advantageously using printing machines of conventional design, forexample intaglio printing machines, rotary screen printing machines,roller printing machines and flat screen printing machines.

In one interesting embodiment of the process according to the invention,the textile fibre material is printed by the transfer printing orthermoprinting process. In that process, first a carrier material, forexample a web of paper, is printed and then, in a further step, theprint is transferred from the carrier material to the textile fibrematerial. Transfer printing or thermoprinting processes are known to theperson skilled in the art, for example from N. L. Moore, J. Soc. Dyersand Colourists, 09/1974, pages 318 to 325.

After being printed, the fibre material is advantageously dried,preferably at temperatures of from 80 to 120° C.

Fixing of the print can then be carried out, for example, by a heattreatment, which is preferably performed at a temperature of from 120 to190° C. Fixing preferably takes from 1 to 8 minutes in that case.

Fixing can also be carried out, however, with ionising radiation or byirradiation with UV light.

When ultraviolet radiation is used, the presence of a photoinitiator isgenerally required. The photoinitiator absorbs the radiation in order toproduce free radicals that initiate the polymerisation. Suitablephotoinitiators are known to the person skilled in the art.

Following fixing, the dyed or printed fibre material may, if desired, bewashed and dried in the usual manner.

The process according to the invention is suitable for dyeing orprinting very diverse fibre materials, such as wool, silk, cellulose,polyacrylonitrile, polyamide, aramide, polyolefins, for examplepolyethylene or polypropylene, polyesters or polyurethane.

Preference is given to fibre materials containing cellulose. Suitablefibre materials containing cellulose are materials that consist entirelyor partially of cellulose. Examples are natural fibre materials, such ascotton, linen or hemp, regenerated fibre materials, such as, forexample, viscose, polynosic or cuprammonium rayon. Also suitable aremixed fibre materials containing cellulose, that is to say, mixtures ofcellulose and other fibres, especially cotton/polyester fibre materials.

Wovens, knits or webs of those fibres are mainly used.

Using the process according to the invention it is possible to obtaintextiles whose colour changes in dependence upon the viewing angle(“flop effect”). In particular, the gloss pigments not having the TiO₂coating, which consist only of silicon and oxygen, are, by virtue of thefact that they are free of heavy metals, outstandingly suitable fortextile applications.

The colorations and prints obtainable by the process according to theinvention are especially distinguished by an extremely high saturationand high goniochromaticity. They also have good general fastnessproperties, such as, for example, good light fastness, good fastness towetting, such as fastness to washing, water, sea water, cross-dyeing andperspiration, good fastness to chlorine, fastness to rubbing, fastnessto ironing and fastness to pleating.

The following Examples serve to illustrate the invention withoutlimiting the scope thereof. Unless stated otherwise, temperatures aregiven in degrees Celsius, parts therein are parts by weight andpercentages are percentages by weight. The relationship between parts byweight and parts by volume is the same as that between kilograms andlitres.

PREPARATION EXAMPLES 1A TO 1E (GLOSS PIGMENTS A)

A layer of approximately 50 nm of NaCl is vapour-deposited onto ametallic carrier in a vacuum chamber at a pressure of less thanapproximately 10⁻² Pa. Then, at the same pressure, the followingmaterials are successively vapour-deposited: Si, SiO and Si, whereby afilm having the layer structure SiO_(x)/SiO_(y)/SiO_(x) is produced onthe metal belt. The separating agent is then dissolved in water,whereupon flakes come away from the substrate. At atmospheric pressure,the resulting suspension is concentrated by filtration and rinsedseveral times with deionised water in order to remove Na⁺ and Cl⁻ ionsthat are present. That is followed by the steps of drying and, whereapplicable, heating of the plane-parallel SiO_(x) structures in the formof loose material at 200° C. for two hours in an oven through which airheated to 200° C. is passed. On heating of the platelets, an SiO₂ layerapproximately 20 nm thick is formed on the surface, on the SiO_(x)layer. After cooling, comminution and grading by air-sieving are carriedout.

In accordance with the process described above, the products listed inthe following Table 1 are obtained: TABLE 1 SiO_(0.2) SiO₂ SiO_(0.2)Example [nm] [nm] [nm] Colour Colour change 1a 45 160 45 matt orangematt orange to matt yellow-green 1b 45 240 45 matt blue- matt blue-greento green matt violet 1c 45 260 45 glossy blue- glossy blue-green greento glossy violet 1d 45 280 45 glossy green glossy green to violet 1e 45440 45 glossy glossy yellow-green yellow-green to glossy green

The pigments obtained in accordance with Preparation Example 1 exhibit acolour change when the viewing angle is changed.

PREPARATION EXAMPLES 2A TO 2K (GLOSS PIGMENTS B)

2a) A graphite crucible containing silicon granules (purity: 95% byweight Si) and one containing sodium chloride are placed as materials tobe vapour-deposited in a vacuum vapour-deposition chamber having arotating aluminium drum as the target. At a pressure of approximately0.1 Pa, first 100 nm of sodium chloride are vapour-deposited and then,in the course of 100 seconds, 100 nm of silicon in the form of alow-oxide compound (by reaction with some of the oxygen that ispresent). The coated aluminium drum is immersed in water; the product,which breaks up into particles, is recovered by filtration, rinsed withwater and dried in air at 150° C. A brilliant green power having agoniochromatic effect is obtained.

2b) The procedure is analogous to Example 2a, but 120 nm of silicon inthe form of a low-oxide compound are vapour-deposited. A brilliantorange-red powder having a goniochromatic effect is obtained.

2c) The procedure is analogous to Example 2a, but 125 nm of silicon inthe form of a low-oxide compound are vapour-deposited. A brilliant redpowder having a goniochromatic effect is obtained.

2d) The procedure is analogous to Example 2a, but 130 nm of silicon inthe form of a low-oxide compound are vapour-deposited. A brilliantpurple powder having a goniochromatic effect is obtained.

2e) The procedure is analogous to Example 2a, but first 100 nm of sodiumchloride are vapour-deposited and then 25 nm of silicon monoxide, 90 nmof silicon in the form of a low-oxide compound and again 25 nm ofsilicon monoxide. Heating is subsequently carried out in air at 250° C.for 1 hour, the outer layer being converted into silicon dioxide and atthe same time increasing in thickness. A brilliant purple powder havinga strong goniochromatic effect is obtained.

2f) The procedure is analogous to Example 2e, but first 100 nm of sodiumchloride are vapour-deposited and then 50 nm of TiO₂, 25 nm of silicondioxide, 50 nm of silicon in the form of a low-oxide compound, 25 nm ofsilicon dioxide and 50 nm of TiO₂. A violet powder having a stronggoniochromatic effect is obtained.

2g) The procedure is analogous to Example 2e, but first 100 nm of sodiumchloride are vapour-deposited and then 50 nm of TiO₂, 50 nm of silicondioxide, 50 nm of silicon in the form of a low-oxide compound, 50 nm ofsilicon dioxide and 50 nm of TiO₂. A blue powder having a stronggoniochromatic effect is obtained.

2h) The procedure is analogous to Example 2e, but first 100 nm of sodiumchloride are vapour-deposited and then 50 nm of TiO₂, 100 nm of silicondioxide, 50 nm of silicon in the form of a low-oxide compound, 100 nm ofsilicon dioxide and 50 nm of TiO₂. A yellow-green powder having highcolour saturation and a strong goniochromatic effect is obtained.

2i) The procedure is analogous to Example 2e, but first 100 nm of sodiumchloride are vapour-deposited and then 100 nm of TiO₂, 100 nm of silicondioxide, 100 nm of silicon in the form of a low-oxide compound, 100 nmof silicon dioxide and 100 nm of TiO₂. A red-violet powder having astrong goniochromatic effect is obtained.

2j) The procedure is analogous to Example 2e, but first 100 nm of sodiumchloride are vapour-deposited and then 100 nm of TiO₂, 50 nm of silicondioxide, 100 nm of silicon in the form of a low-oxide compound, 50 nm ofsilicon dioxide and 100 nm of TiO₂. An orange powder having a stronggoniochromatic effect is obtained.

2k) The procedure is analogous to Example 2e, but first 100 nm of sodiumchloride are vapour-deposited and then 100 nm of TiO₂, 25 nm of silicondioxide, 100 nm of silicon in the form of a low-oxide compound, 25 nm ofsilicon dioxide and 100 nm of TiO₂. A yellow powder having a stronggoniochromatic effect is obtained.

Example 1

A stock thickening is prepared by mixing the following components: 600parts water 5 parts deaerating agent (Lyoprint ® AP)* 5 parts ammonia(25% ig) 100 parts acrylate-based binder (Alcoprint ® PB-HC)* 14 partsthickener (Alcoprint ® PTP)**products of Ciba Specialty Chemicals

The thickener is homogenised in the mixture by means of a high-speedstirrer.

The viscosity of the above-mentioned stock thickening is approximately14,000 mPas±10% (Brookfield RVT, 25° C., 20 rev/min, spindle 5).

A printing paste is produced by incorporating 0.8 part of the glosspigment from Preparation Example 1a into 99.2 parts of the above stockthickening.

A cotton fabric is printed with the printing paste on a Zimmer flatscreen printing machine (screen 64, squeegee 12 mm, p=6, v=3). The printis dried at 120° C. for 2 minutes and then fixed at 150° C. for 5minutes. A print having a strong goniochromatic effect from matt orangeto matt yellow-green and good fastness to wetting and light is obtained.

Examples 2 to 5

The procedure is the same as in Example 1, except that, instead of thequantity of gloss pigment A given therein, an identical quantity of oneof the gloss pigments A given in the following Table 2 is used, likewiseproducing prints having a strong goniochromatic effect and good fastnessto wetting and light. TABLE 2 Ex. Gloss pigment A from Ex. Colour 2 1bmatt blue-green to matt violet 3 1c glossy blue-green to glossy violet 41d glossy green to violet 5 1e glossy yellow-green to glossy green

Examples 6 to 16

The procedure is the same as in Example 1, except that, instead of thequantity of gloss pigment A given therein, an identical quantity of oneof the gloss pigments B from Preparation Examples 2a, 2b, 2c, 2d, 2e,2f, 2g, 2h, 2i, 2j and 2k is used, likewise producing prints having astrong goniochromatic effect and good fastness to wetting and light.

Example 17

A stock solution is prepared by mixing the following components: 676parts water 10 parts defoamer (DF-66 25%) 5 parts dispersant (Albegal ®A)* 10 parts thickener (Irgapadol ® MP)* 100 parts binder (Irgaphor ®SPD-B)* 9 parts fabric softener (Avivan ® MS)**products of Ciba Specialty Chemicals

A cotton fabric is padded with a dyeing composition comprising 80 partsof the stock solution mentioned above, 0.8 part of the gloss pigmentfrom Preparation Example 1a and 19.2 parts water. The impregnated fabricis dried and fixed at from 140 to 170° C. for from 2 to 5 minutes.Alternatively, drying and fixing can also be carried out at 185° C. for1 minute. A coloration having a strong goniochromatic effect from mattorange to matt yellow-green and good fastness to wetting and light isobtained.

Examples 18 to 32

The procedure is the same as in Example 17, except that, instead of thequantity of gloss pigment from Preparation Example 1a given therein, anidentical quantity of one of the gloss pigments from PreparationExamples 1b, 1c, 1d, 1e, 2a, 2b, 2c, 2d, 2e, 2f, 2g, 2h, 2i, 2j and 2kis used, likewise producing colorations having a strong goniochromaticeffect and good fastness to wetting and light.

Example 33

A stock solution is prepared by mixing the following components: 643parts water 10 parts defoamer (DF-66 25%) 25 parts thickener(Irgapadol ® MP)* 60 parts fabric softener (Avivan ® MS)* 2 partswetting agent (Cibaflow ® PAD)* 20 parts binder (Cibatex ® EM)* 40 partsbinder (Dicrylan ® AM)**products of Ciba Specialty Chemicals

A cotton fabric is padded with a dyeing composition comprising 80 partsof the stock solution mentioned above, 0.8 part of the gloss pigmentfrom Preparation Example 1a and 19.2 parts water. The impregnated fabricis dried and fixed at from 140 to 170° C. for from 2 to 5 minutes.Alternatively, drying and fixing can also be carried out at 185° C. for1 minute. A coloration having a strong goniochromatic effect from mattorange to matt yellow-green and good fastness to wetting and light isobtained.

Examples 34 to 48

The procedure is the same as in Example 33, except that, instead of thequantity of gloss pigment from Preparation Example 1a, an identicalquantity of one of the gloss pigments from Preparation Examples 1b, 1c,1d, 1e, 2a, 2b, 2c, 2d, 2e, 2f, 2g, 2h, 2i, 2j and 2k is used, likewiseproducing colorations having a strong goniochromatic effect and goodfastness to wetting and light.

1. A process for dyeing or printing textile fibre materials, wherein agloss pigment A or B is used comprising A(a) a core consisting of asubstantially transparent or metallically reflecting material and A(b)at least one coating substantially consisting of one or more siliconoxides wherein the molar ratio of oxygen to silicon is on average from0.03 to 0.95, or B(a) a core substantially consisting of one or moresilicon oxides wherein the molar ratio of oxygen to silicon is onaverage from 0.03 to 0.95.
 2. A process according to claim 1, whereinthe core A(a) of gloss pigment A consists of mica, SiO_(y) wherein y isfrom 0.95 to 1.8, SiO₂ or an SiO₂/TiO₂ mixture.
 3. A process accordingto claim 1, wherein the core A(a) of gloss pigment A is selected fromAg, Al, Au, Cu, Cr, Ge, Mo, Ni, Si, Ti, Zn, alloys thereof, graphite,Fe₂O₃ and MoS₂.
 4. A process according to claim 1, wherein the glosspigment A has the following layer structure:SiO₂/SiO_(x)/SiO_(y)/SiO_(x)/SiO₂, SiO₂/SiO_(x)/SiO₂/SiO_(x)/SiO₂,SiO₂/SiO_(x)/Al/SiO_(x)/SiO₂, TiO₂/SiO₂/SiO_(x)/SiO₂/SiO_(x)/SiO₂/TiO₂or TiO₂/SiO₂/SiO_(x)/Al/SiO_(x)/SiO₂/TiO₂, wherein x is from 0.03 to0.95 and y is from 0.95 to 1.8.
 5. A process according to claim 4,wherein the gloss pigment A has the following layer structure:SiO₂/SiO_(x)/SiO_(y)/SiO_(x)/SiO₂, SiO₂/SiO_(x)/SiO₂/SiO_(x)/SiO₂ orTiO₂/SiO₂/SiO_(x)/SiO₂/SiO_(x)/SiO₂/TiO₂, wherein x is from 0.03 to 0.95and y is from 0.95 to 1.8, the core is a platelet having an averagediameter of from 1 to 50 μm and a thickness of from 20 to 500 nm, thethickness of the SiO_(x) layer is from 5 to 200 nm, the thickness of theSiO_(y) or SiO₂ layer is from 1 to 200 nm, and the thickness of the TiO₂layer is from 1 to 180 nm.
 6. A process according to claim 1, whereinthe core B(a) of gloss pigment B has a thickness of from 20 to 350 nm.7. A process according to claim 1, wherein there is applied to the coreB(a) of gloss pigment B a layer B(b) having a thickness of from 0 to 500nm, comprising from 17 to 51 atom % silicon bonded to more than 95 atom% oxygen, based on 100 atom % silicon.
 8. A process according to claim1, wherein there is applied to the core B(a) of gloss pigment B a layerB(c) having a thickness of from 0 to 300 nm, that has a transparency offrom 50 to 100% and a complex refractive index n+ik satisfying thecondition √{square root over (n²+k²)}≧1.5 at the wavelength of maximumvisible reflection of the particles, and that substantially consists ofcarbon, an organic compound, a metal, a dielectric or a mixture thereof.9. A process according to claim 7, wherein there is applied to the layerB(b) of gloss pigment B a layer B(c) having a thickness of from 0 to 300nm, that has a transparency of from 50 to 100% and a complex refractiveindex n+ik satisfying the condition √{square root over (n²+k²)}≧1.5 atthe wavelength of maximum visible reflection of the particles, and thatsubstantially consists of carbon, an organic compound, a metal, adielectric or a mixture thereof.
 10. A process according to claim 1,wherein the textile fibre material is printed.
 11. A process accordingto claim 1, wherein the textile fibre material is printed by thetransfer printing or thermoprinting process.
 12. A process according toclaim 1, wherein the core A(a) of gloss pigment A is Al.
 13. A processaccording to claim 7, wherein the core B(a) of gloss pigment B has athickness of from 20 to 350 nm.
 14. A process according to claim 8,wherein the core B(a) of gloss pigment B has a thickness of from 20 to350 nm.
 15. A process according to claim 9, wherein the core B(a) ofgloss pigment B has a thickness of from 20 to 350 nm.
 16. A processaccording to claim 2, wherein the textile fibre material is printed. 17.A process according to claim 9, wherein the textile fibre material isprinted.
 18. A process according to claim 13, wherein the textile fibrematerial is printed.
 19. A process according to claim 4, wherein thetextile fibre material is printed by the transfer printing orthermoprinting process.
 20. A process according to claim 13, wherein thetextile fibre material is printed by the transfer printing orthermoprinting process.